The present invention relates generally to crosslinked cellulosic fibers and more particularly, to cellulosic fibers crosslinked with polymeric polycarboxylic acid crosslinking agents, methods for producing such fibers, and absorbent structures containing polymeric polycarboxylic acid crosslinked fibers.
Cellulose products such as absorbent sheets and other structures are composed of cellulose fibers which, in turn, are composed of individual cellulose chains. Commonly, cellulose fibers are crosslinked to impart advantageous properties such as increased absorbent capacity, bulk, and resilience to structures containing cellulose fibers. High-bulk fibers are generally highly crosslinked fibers characterized by high absorbent capacity and high resilience.
Crosslinked cellulose fibers and methods for their preparation are widely known. Tersoro and Willard, Cellulose and Cellulose Derivatives, Bikales and Segal, eds., Part V, Wiley-InterScience, New York, (1971), pp. 835-875. Most commonly, the term xe2x80x9ccrosslinked cellulose fiberxe2x80x9d refers to a cellulose fiber having intrafiber crosslinks, i.e., crosslinks between individual cellulose chains within a single cellulose fiber. Generally, intrafiber crosslinks are formed by curing a crosslinking agent in the presence of the fibers. xe2x80x9cCuringxe2x80x9d refers to covalent bond formation (i.e., crosslink formation) between the crosslinking agent and the fiber. Crosslinking agents are generally bifunctional compounds, and in the context of cellulose crosslinking, these agents covalently couple a hydroxy group of one cellulose chain to another hydroxy group on a neighboring cellulose chain. Many crosslinking agents have been utilized in cellulose crosslinking achieving varying degrees of success.
Common cellulose crosslinking agents include aldehyde and urea-based formaldehyde addition products. See, for example, U.S. Pat. Nos. 3,224,926; 3,241,533; 3,932,209; 4,035,147; and 3,756,913. While these crosslinking agents have been widely used in some environments, their applicability to absorbent products that contact human skin (e.g., diapers) has been limited by safety concerns. These crosslinkers are known to cause irritation to human skin. Moreover, formaldehyde, which persists in formaldehyde-crosslinked products, is a known health hazard and has been listed as a carcinogen by the EPA. Accordingly, the disadvantages associated with formaldehyde and other formaldehyde-derived crosslinking agents has prompted the development of safer alternatives.
Other aldehyde crosslinking agents are also known. For example, dialdehyde crosslinking agents (i.e., C2-C8 dialdehydes and preferably glutaraldehyde) have also been utilized in the production of absorbent structures containing crosslinked cellulose fibers. See, for example, U.S. Pat. Nos. 4,689,118 and 4,822,453. While these dialdehyde crosslinkers appear to overcome the health risks associated with formaldehyde crosslinkers, these crosslinking agents suffer from commercial disadvantages related to the costs of producing dialdehyde crosslinked fibers.
Cellulose has also been crosslinked by carboxylic acid crosslinking agents. Certain polycarboxylic acids have been used to provide absorbent structures that have the polycarboxylic acid reacted with fibers in the form of intrafiber crosslink bonds. For example, U.S. Pat. Nos. 5,137,537, 5,183,707, and 5,190,563 describe the use of C2-C9 polycarboxylic acids crosslinking agents. These C2-C9 polycarboxylic acids are low molecular weight polycarboxylic acids that contain at least three carboxyl groups, and have from two to nine carbons in the chain or ring separating two of the carboxyl groups. Exemplary C2-C9 polycarboxylic acids include 1,2,3-tricarboxypropane, 1,2,3,4-tetracarboxybutane, and oxydisuccinic acid. A particularly preferred C2-C9 polycarboxylic acid is 2-hydroxy-1,2,3-tricarboxypropane, also known as citric acid. Unlike the aldehyde-based crosslinking agents noted above, these polycarboxylic acids are nontoxic and, for the preferred polycarboxylic acid citric acid, the crosslinking agent is commercially available at relatively low cost. Moreover, while the aldehyde-based crosslinking agents form relatively unstable acetal crosslinked bonds, C2-C9 polycarboxylic acid crosslinking agents provide relatively stable ester crosslinks.
While some of the disadvantages associated with the crosslinking agents noted above have been overcome by the development and utilization of new and improved crosslinking agents, crosslinking agents are generally characterized by their relatively narrow cure temperature range. The length of time at a particular cure temperature is also a factor in crosslinking fibers. The narrow cure temperature range of traditional crosslinking agents, such as those noted above, is due to their chemical reactivity. Most crosslinking agents have bifunctional reactivity and will undergo crosslinking at a temperature sufficient to cause the functional groups of the crosslinking agent (e.g., the aldehyde group of formaldehyde, or a carboxylic acid group of citric acid) to react with crosslink sites of the cellulose fiber (i.e., a hydroxy group). Generally, crosslinking occurs rapidly once a temperature sufficient to effect bond formation between the agent and fibers is reached.
Accordingly, there is a need in the art for a crosslinking agent that allows for greater flexibility in the production of crosslinked fibers having specific, desirable properties. More specifically, there exists a need for a safe and economical crosslinking agent curable over a wide temperature range to provide crosslinked fibers having a correspondingly wide range of crosslinking and associated advantageous absorbent properties.
Despite the advantages that polycarboxylic acid crosslinking agents provide, certain crosslinked cellulosic fibers, particularly cellulosic fibers crosslinked with low molecular weight polycarboxylic acids such as citric acid, tend to lose their crosslinks over time and revert to uncrosslinked fibers. For example, citric acid crosslinked fibers show a considerable loss of crosslinks on storage. Such a reversion of crosslinking generally defeats the purpose of fiber crosslinking, which is to increase the fiber""s bulk and capacity. Thus, the useful shelf-life of fibers crosslinked with these polycarboxylic acids is relatively short and renders the fibers somewhat limited in their utility.
The loss of crosslinking results in a loss of the advantageous properties imparted to the fibers by crosslinking. Aged fibers, that is, fibers that have been subject to crosslinking reversion, can be characterized as having relatively lower bulk, diminished absorbent capacity, and lower liquid acquisition capability compared to the same fibers as originally formed.
Accordingly, there exists a need for stable intrafiber crosslinked cellulose fibers that offer the absorbent properties and advantages afforded by traditional crosslinked fibers and that also retain their intrafiber crosslinks over time and in storage to provide a crosslinked fiber having a substantial useful shelf-life. The present invention seeks to fulfill these needs and provides further related advantages.
In one aspect, the present invention provides individualized, chemically crosslinked cellulosic fibers comprising individualized cellulosic fibers intrafiber crosslinked with a polymeric polycarboxylic acid crosslinking agent. In one embodiment, the polymeric polycarboxylic acid crosslinking agent is an acrylic acid polymer and, in another embodiment, the polymeric polycarboxylic acid crosslinking agent is a maleic acid polymer. The polymeric polycarboxylic acid crosslinked fibers of the present invention are characterized as having high bulk, increased absorbent capacity, and enhanced liquid acquisition rates relative to noncrosslinked cellulosic fibers and fibers crosslinked with traditional crosslinking agents.
In another aspect of the present invention, a method for forming individualized, chemically intrafiber crosslinked cellulosic fibers is provided. In the method, a polymeric polycarboxylic acid crosslinking agent is applied to a mat of cellulosic fibers, the mat is then separated into unbroken individual fibers, and the individualized fibers are then dried and the crosslinking agent cured to form intrafiber crosslinks. Alternatively, in another embodiment, the fibers can be crosslinked (e.g., partially) in the mat prior to separation of the fibers and the formation of individual fibers.
Another aspect of the present invention provides a method for producing crosslinked fibers having absorbent properties that are dependent on the temperature at which the fibers are cured. In the method, the fibers are crosslinked with a polymeric polycarboxylic acid at a cure temperature between about 320xc2x0 F. and about 380xc2x0 F.
In yet another aspect, a method for forming crosslinked fibers having stable crosslinks is provided. In the method, cellulosic fibers are crosslinked with a polymeric polycarboxylic acid crosslinking agent.
In still another aspect, the present invention provides a method for forming crosslinked cellulosic fibers having a knot level significantly lower than other conventionally crosslinked fibers. In the method, cellulosic fibers are crosslinked with a polymaleic acid polymer crosslinking agent.
The present invention also provides absorbent structures that contain the individualized, polymeric polycarboxylic acid crosslinked fibers of this invention, and absorbent constructs incorporating such structures.
The present invention is directed to a polymeric polycarboxylic acid crosslinking agent for cellulose fibers, polymeric polycarboxylic acid crosslinked cellulose fibers, products containing these crosslinked fibers, and methods related to these fibers.
In one aspect, the present invention provides individualized, chemically crosslinked cellulosic fibers that have been intrafiber crosslinked with a polymeric polycarboxylic acid crosslinking agent. As used herein, the term xe2x80x9cpolymeric polycarboxylic acidxe2x80x9d refers to a polymer having multiple carboxylic acid groups available for forming ester bonds with cellulose (i.e., crosslinks). Generally, the polymeric polycarboxylic acid crosslinking agents useful in the present invention are formed from monomers and/or comonomers that include carboxylic acid groups or functional groups that can be converted into carboxylic acid groups. Suitable crosslinking agents useful in forming the crosslinked fibers of the present invention include polyacrylic acid polymers, polymaleic acid polymers, copolymers of acrylic acid, copolymers of maleic acid, and mixtures thereof. Other suitable polymeric polycarboxylic acids include commercially available polycarboxylic acids such as polyaspartic, polyglutamic, poly(3-hydroxy)butyric acids, and polyitaconic acids. As used herein, the term xe2x80x9cpolyacrylic acid polymerxe2x80x9d refers to polymerized acrylic acid (i.e., polyacrylic acid); xe2x80x9ccopolymer of acrylic acidxe2x80x9d refers to a polymer formed from acrylic acid and a suitable comonomer, copolymers of acrylic acid and low molecular weight monoalkyl substituted phosphinates, phosphonates, and mixtures thereof; the term xe2x80x9cpolymaleic acid polymerxe2x80x9d refers to polymerized maleic acid (i.e., polymaleic acid) or maleic anhydride; and xe2x80x9ccopolymer of maleic acidxe2x80x9d refers to a polymer formed from maleic acid (or maleic anhydride) and a suitable comonomer, copolymers of maleic acid and low molecular weight monoalkyl substituted phosphinates, phosphonates, and mixtures thereof.
Polyacrylic acid polymers include polymers formed by polymerizing acrylic acid, acrylic acid esters, and mixtures thereof. Polymaleic acid polymers include polymers formed by polymerizing maleic acid, maleic acid esters, maleic anhydride, and mixtures thereof. Representative polyacrylic and polymaleic acid polymers are commercially available from, for example, the Rohm and Haas Company.
Examples of suitable polyacrylic acid copolymers include poly(acrylamide-co-acrylic acid), poly(acrylic acid-co-maleic acid), poly(ethylene-co-acrylic acid), and poly(1-vinylpyrolidone-co-acrylic acid), as well as other polyacrylic acid derivatives such as poly(ethylene-co-methacrylic acid) and poly(methyl methacrylate-co-methacrylic acid). Suitable polymaleic acid copolymers include poly(methyl vinyl ether-co-maleic acid), poly(styrene-co-maleic acid), and poly(vinyl chloride-co-vinyl acetate-co-maleic acid). The representative polycarboxylic acid copolymers noted above are available in various molecular weights and ranges of molecular weights from commercial sources.
Generally, the polymeric polycarboxylic acids useful in the present invention include polymers having molecular weights in the range of from about 500 to about 40,000, and preferably from about 600 to about 10,000 grams/mole. Polyacrylic acid polymers preferably have molecular weights in the range of from about 1500 to about 15,000. Polymaleic acid polymers preferably have molecular weights in the range of from about 600 to about 1500. In contrast to the relatively high molecular weight polymaleic polycarboxylic acid crosslinking agents of the present invention, the C2-C9 polycarboxylic acids noted above have molecular weights no greater than about 350 g/mole.
As noted above, polycarboxylic acid copolymers are also useful for forming the crosslinked cellulose fibers of the present invention. Suitable polycarboxylic acid copolymers include copolymers of acrylic acid (i.e., acrylic acid copolymers) and copolymers of maleic acid (i.e., maleic acid copolymers) and have molecular weights ranging from about 500 to about 40,000, and more preferably from about 600 to about 2000 grams/mole. The weight ratio of acrylic or maleic acid to comonomer for these copolymers can range from about 10:1 to about 1:1, and more preferably from about 5:1 to about 2:1.
Suitable comonomers for forming polyacrylic and polymaleic acid copolymers include any comonomer that, when copolymerized with acrylic acid or maleic acid (or their esters), provides a polycarboxylic acid copolymer crosslinking agent that produces crosslinked cellulose fibers having the advantageous properties of bulk, absorbent capacity, liquid acquisition rate, and stable intrafiber crosslinks. Representative comonomers include, for example, ethyl acrylate, vinyl acetate, acrylamide, ethylene, vinyl pyrrolidone, methacrylic acid, methylvinyl ether, styrene, vinyl chloride, itaconic acid, and tartrate monosuccinic acid. Preferred comonomers include vinyl acetate, methacrylic acid, methylvinyl ether, and itaconic acid. Polyacrylic and polymaleic acid copolymers prepared from representative comonomers noted above are available in various molecular weights and ranges of molecular weights from commercial sources. In a preferred embodiment, the polycarboxylic acid copolymer is a copolymer of acrylic and maleic acids.
The polycarboxylic acid polymers useful in forming the crosslinked fibers of the present invention include self-catalyzing polycarboxylic acid polymers. As used herein, the term xe2x80x9cself-catalyzing polycarboxylic acid polymerxe2x80x9d refers to a polycarboxylic acid polymer derivative that forms crosslinks with cellulose fibers at a practical rate at convenient cure temperatures without the aid of a crosslinking catalyst. Preferably, the self-catalyzing polycarboxylic acid crosslinking agent is a copolymer of either acrylic acid or maleic acid and low molecular weight monoalkyl substituted phosphinates and phosphonates. These copolymers can be prepared with hypophosphorous acid and its salts, for example, sodium hypophosphite, and/or phosphorus acids as chain transfer agents.
The polycarboxylic acid polymers and copolymers described above can be used alone, in combination, or in combination with other crosslinking agents known in the art.
Those knowledgeable in the area of polycarboxylic acid polymers will recognize that the polycarboxylic acid polymer crosslinking agents described above may be present in a variety of forms, such as the free acid form, and salts thereof. Although the free acid form is preferred, it will be appreciated that all forms of the acid are included within the scope of the present invention. For embodiments of the invention that include a polymaleic acid polymer, a low pH polymaleic acid having a pH from about 2 to about 4 is preferred.
Cellulose fiber crosslinking with the polymeric polycarboxylic acid crosslinking agents described above can be accomplished at practical rates without a catalyst provided that the pH of the crosslinking reaction is maintained at acidic pH (i.e., pH ranges from about 1 to about 5). The effect of crosslinking solution pH on absorbent capacity of representative polymaleic acid crosslinked fibers formed in accordance with the present invention is described in Example 8. Preferably the pH of the crosslinking solution is maintained at a pH in the range of from about 2 to about 4.
Alternatively, the polymeric polycarboxylic acid crosslinking agents can be used with a crosslinking catalyst to accelerate the bonding reaction between the crosslinking agent and the cellulose fiber to provide the crosslinked cellulose fibers of this invention. Suitable crosslinking catalysts include any catalyst that increases the rate of ester bond formation between the polycarboxylic acid crosslinking agent and cellulose fibers. Preferred crosslinking catalysts include alkali metal salts of phosphorous containing acids such as alkali metal hypophosphites, alkali metal phosphites, alkali metal polyphosphonates, alkali metal phosphates, and alkali metal sulfonates. Particularly preferred catalysts include alkali metal polyphosphonates such as sodium hexametaphosphate and alkali metal hypophosphites such as sodium hypophosphite. The crosslinking catalyst is typically present in the crosslinking reaction in an amount in the range of from about 5 to about 20 weight percent of the crosslinking agent. Preferably, the catalyst is present in an amount of about 10 percent by weight of the crosslinking agent. A representative method for forming crosslinked cellulosic fibers with the aid of a catalyst is described in Example 2.
In such a method, the crosslinking catalyst is applied to the cellulose fibers in a manner analogous to application of the crosslinking agent to the fibers as described above. The crosslinking catalyst may be applied to the fibers prior to, after, or at the same time as the crosslinking agent is applied to the fibers. Accordingly, the present invention provides a method of producing crosslinked fibers that includes curing the crosslinking agent in the presence of a crosslinking catalyst.
Generally, the crosslinking catalyst promotes the formation of ester bonds between the polycarboxylic acid and the cellulose fiber. The catalyst is effective in increasing the degree of crosslinking (i.e., the number of ester bonds formed) at a given cure temperature. For example, as illustrated in Example 2, the level of crosslinking (as assessed by absorbent capacity) achieved at 360xc2x0 F. without a catalyst is comparable to the crosslinking level achieved with a catalyst at 330xc2x0 F. In other words, at a given cure temperature, the use of a crosslinking catalyst provides increased crosslinking. The preparation and properties of cellulose fibers crosslinked with a representative polycarboxylic acid crosslinking agent and crosslinking catalyst are described in Example 2.
The crosslinked cellulose fibers of the present invention have an effective amount of a polycarboxylic acid crosslinking agent reacted with the fibers to form intrafiber crosslinks. As used herein, xe2x80x9ceffective amount of a polycarboxylic acid polymer crosslinking agentxe2x80x9d refers to an amount of crosslinking agent sufficient to provide an improvement in the absorbent properties (e.g., capacity, bulk, acquisition rate) or physical properties (e.g., stable intrafiber crosslink, low knot level) of the crosslinked fibers themselves, relative to conventional, uncrosslinked fibers, or fibers crosslinked with other crosslinking agents. Generally, the cellulose fibers are, treated with a sufficient amount of a crosslinking agent such that an effective amount of crosslinking agent is reacted with the fibers.
The polymeric polycarboxylic acid crosslinking agent is preferably present on the fibers in an amount from about 1 to about 10% by weight of the total weight of the fibers. More preferably, the polymeric polycarboxylic acid is present in an amount from about 2 to about 8% by weight of the total fibers and, in a more preferred embodiment, from about 3 to about 6% by weight of the total fibers. The effect of amount of polymeric polycarboxylic acid on fiber bulk, capacity, and liquid acquisition rate is described in Examples 1, 5, and 6. Generally, increasing the amount of crosslinking agent on the fibers increases fiber bulk and capacity. Fibers crosslinked with 3-4% polymaleic acid generally have a liquid acquisition rate significantly greater than fibers similarly crosslinked with a representative urea-based crosslinking agent, DMDHEU.
As noted above, the present invention relates to cellulose fibers that are chemically intrafiber crosslinked with a polymeric polycarboxylic acid crosslinking agent. Although available from other sources, cellulosic fibers are derived primarily from wood pulp. Suitable wood pulp fibers for use with the invention can be obtained from well-known chemical processes such as the Kraft and sulfite processes, with or without subsequent bleaching. The pulp fibers may also be processed by thermomechanical, chemithermomechanical methods, or combinations thereof. The preferred pulp fiber is produced by chemical methods. Ground wood fibers, recycled or secondary wood pulp fibers, and bleached and unbleached wood pulp fibers can be used. The preferred starting material is prepared from long fiber coniferous wood species, such as southern pine, Douglas fir, spruce, and hemlock. Details of the production of wood pulp fibers are well-known to those skilled in the art. These fibers are commercially available from a number of companies, including Weyerhaeuser Company, the assignee of the present invention. For example, suitable cellulose fibers produced from southern pine that are usable with the present invention are available from Weyerhaeuser Company under the designations CF416, NF405, PL416, FR516, and NB416.
The wood pulp fibers useful in the present invention can also be pretreated prior to use with the present invention. This pretreatment may include physical treatment, such as subjecting the fibers to steam, or chemical treatment.
Although not to be construed as a limitation, examples of pretreating fibers include the application of fire retardants to the fibers, and surfactants or other liquids, such as water or solvents, which modify the surface chemistry of the fibers. Other pretreatments include incorporation of antimicrobials, pigments, and densification or softening agents. Fibers pretreated with other chemicals, such as thermoplastic and thermosetting resins also may be used. Combinations of pretreatments also may be employed.
Cellulosic fibers treated with particle binders and/or densification/softness aids known in the art can also be employed in accordance with the present invention. The particle binders serve to attach other materials, such as superabsorbent polymers, as well as others, to the cellulosic fibers. Cellulosic fibers treated with suitable particle binders and/or densification/softness aids and the process for combining them with cellulose fibers are disclosed in the following U.S. patents and patent applications: (1) U.S. Pat. No. 5,543,215, entitled xe2x80x9cPolymeric Binders for Binding Particles to Fibersxe2x80x9d; (2) U.S. Pat. No. 5,538,783, entitled xe2x80x9cNon-Polymeric Organic Binders for Binding Particles to Fibersxe2x80x9d; (3) U.S. Pat. No. 5,300,192, entitled xe2x80x9cWet Laid Fiber Sheet Manufacturing With Reactivatable Binders for Binding Particles to Binders;xe2x80x9d (4) U.S. Pat. No. 5,352,480, entitled xe2x80x9cMethod for Binding Particle to Fibers Using Reactivatable Bindersxe2x80x9d; (5) U.S. Pat. No. 5,308,896, entitled xe2x80x9cParticle Binders for High-Bulk Fibersxe2x80x9d; (6) U.S. Pat. No. 5,589,256, entitled xe2x80x9cParticle Binders that Enhance Fiber Densificationxe2x80x9d; (7) U.S. Pat. No. 5,672,418, entitled xe2x80x9cParticle Bindersxe2x80x9d; (8) U.S. Pat. No. 5,607,759, entitled xe2x80x9cParticle Binding to Fibersxe2x80x9d; (9) U.S. Pat. No. 5,693,411, entitled xe2x80x9cBinders for Binding Water Soluble Particles to Fibersxe2x80x9d; (10) U.S. Pat. No. 5,547,745, entitled xe2x80x9cParticle Bindersxe2x80x9d; (11) U.S. Pat. No. 5,641,561, entitled xe2x80x9cParticle Binding to Fibersxe2x80x9d; and (12) U.S. Pat. No. 5,308,896, entitled xe2x80x9cParticle Binders for High-Bulk Fibers,xe2x80x9d all expressly incorporated herein by reference.
The polymeric polycarboxylic acid crosslinking agent may be applied to the cellulose fibers by any one of a number of methods known in the production of treated fibers. For example, the polymeric polycarboxylic acid can be contacted with the fibers as a fiber sheet is passed through a bath containing the polycarboxylic acid. Alternatively, other methods of applying the polycarboxylic acid, including fiber spray, or spray and pressing, or dipping and pressing with a polycarboxylic acid solution, are also within the scope of the present invention.
Generally, the intrafiber crosslinking cellulose fibers of the present invention can be formed by applying the polymeric polycarboxylic acid crosslinking agent to the cellulose fibers, separating the treated mat into individual fibers, and then curing the crosslinking agent at a temperature sufficient to effect crosslink formation between the polymeric polycarboxylic acid and the cellulose fiber. The polymeric polycarboxylic acid crosslinking agent may be cured by heating the crosslinking agent-treated fiber at a temperature and for a time sufficient to cause crosslinking to occur. The rate and degree of crosslinking depend upon a number of factors including the moisture content of the fibers, temperature, and pH, as well as the amount and type of catalyst. Those skilled in the art will appreciate that time-temperature relationships exist for the curing of the crosslinking agent. Generally, the extent of curing, and consequently the degree of crosslinking, are a function of the cure temperature. The polymeric polycarboxylic acid crosslinking agents of the present invention are preferably cured at temperatures ranging from about 320xc2x0 F. to about 380xc2x0 F. The effect of cure temperature on the bulk and absorbent capacity of representative polymeric polycarboxylic acid crosslinked fibers is described in Examples 1, 2, 3, 5, and 8. Generally, crosslinked fiber bulk and absorbent capacity increase with increasing cure temperature.
In general, the cellulose fibers of the present invention may be prepared by a system and apparatus as described in U.S. Pat. No. 5,447,977 to Young, Sr. et al., which is incorporated herein by reference in its entirety. Briefly, the fibers are prepared by a system and apparatus comprising a conveying device for transporting a mat of cellulose fibers through a fiber treatment zone; an applicator for applying a treatment substance such as a polymeric polycarboxylic acid crosslinking agent from a source to the fibers at the fiber treatment zone; a fiberizer for completely separating the individual cellulose fibers comprising the mat to form a fiber output comprised of substantially unbroken cellulose fibers; and a dryer coupled to the fiberizer for flash evaporating residual moisture and for curing the crosslinking agent(s), to form dried and cured crosslinked fibers.
As used herein, the term xe2x80x9cmatxe2x80x9d refers to any nonwoven sheet structure comprising cellulose fibers or other fibers that are not covalently bound together. The fibers include fibers obtained from wood pulp or other sources including cotton rag, hemp, grasses, cane, husks, cornstalks, or other suitable sources of cellulose fibers that may be laid into a sheet. The mat of cellulose fibers is preferably in an extended sheet form, and may be one of a number of baled sheets of discrete size or may be a continuous roll.
Each mat of cellulose fibers is transported by a conveying device, for example, a conveyor belt or a series of driven rollers. The conveying device carries the mats through the fiber treatment zone.
At the fiber treatment zone the polymeric polycarboxylic acid crosslinking agent is applied to the cellulose fibers. The polymeric polycarboxylic acid is preferably applied to one or both surfaces of the mat using any one of a variety of methods known in the art including spraying, rolling, or dipping. Once the crosslinking agent has been applied to the mat, the crosslinking agent may be uniformly distributed through the mat, for example, by passing the mat through a pair of rollers.
After the fibers have been treated with the crosslinking agent, the impregnated mat is fiberized by feeding the mat through a hammermill. The hammermill serves to separate the mat into its component individual cellulose fibers, which are then blown into a dryer.
The dryer performs two sequential functions; first removing residual moisture from the fibers, and second curing the polymeric polycarboxylic acid crosslinking agent. In one embodiment the dryer comprises a first drying zone for receiving the fibers and for removing residual moisture from the fibers via a flash-drying method, and a second drying zone for curing the crosslinking agent. Alternatively, in another embodiment, the treated fibers are blown through a flash-dryer to remove residual moisture, and then transferred to an oven where the treated fibers are subsequently cured.
The crosslinked cellulose fibers of this invention exhibit advantageous absorbent characteristics including increased absorbent capacity, rate of absorption, bulk, and resilience (springback) relative to noncrosslinked fibers. Generally, the absorbent capacity of fibers (reported in units of grams water/gram fiber), the rate of absorption of water (mL/sec), bulk (cc/g), and resilience (i.e., the extent to which the crosslinked fibers spring back) increase with increasing crosslinking. For the crosslinked fibers of this invention, increased crosslinking may be achieved either by contacting the fiber to be crosslinked with increasing amounts and/or concentrations of crosslinking agent or, alternatively, by increasing the temperature at which the polymaleic acid treated fibers are cured. The preparation and some properties of some representative polymeric polycarboxylic acid crosslinked cellulose fibers of the invention are described in Example 1 (polyacrylic acid crosslinked fibers) and Examples 4-5 (polymaleic acid crosslinked fibers).
As noted above, the absorbent characteristics of crosslinked cellulose fibers formed in accordance with this invention are generally affected by the extent of crosslinking by the polymeric polycarboxylic acid crosslinking agent. Furthermore, it has been discovered that the extent of crosslinking by the polymeric polycarboxylic acid, and consequently the fibers"" resulting absorbent properties can be controlled by the temperature used to cure the treated fibers (i.e., to cause ester bond formation). At higher cure temperature, more ester bonds are formed between the polymeric polycarboxylic acid and the fiber, and greater crosslinking results.
Thus, in another aspect, the present invention provides a method for forming crosslinked cellulosic fibers having absorbent properties that are dependent upon cure temperature. In the method, the crosslinked fibers are generally prepared as described above using a polymeric polycarboxylic acid crosslinking agent and then cured at a cure temperature in the range of from about 320xc2x0 F. to about 380xc2x0 F., the particular cure temperature selected to achieve the desired absorbent capacity, bulk, springback, and liquid acquisition rate characteristics. The effect of cure temperature variation on the properties of polyacrylic acid crosslinked fibers is described in Examples 1 and 2, and the effect of cure temperature of polymaleic acid crosslinked fibers is described in Example 5. As noted above, increasing cure temperature generally results in crosslinked fibers having increased bulk and absorbent capacity.
The polymeric polycarboxylic acid crosslinked fibers of the invention may be formed into sheets or mats having high absorbent capacity, bulk, and resilience. For example, these crosslinked fibers may be combined with other fibers including other crosslinked and noncrosslinked fibers. The sheets and mats comprised of polycarboxylic acid crosslinked fibers may be incorporated into a variety of absorbent products including, for example, tissue sheets, disposable diapers, sanitary napkins, tampons, and bandages.
The polymeric polycarboxylic acid crosslinked fibers formed in accordance with the present invention exhibit a density that remains substantially unchanged over the lifetime of fibrous webs prepared from these fibers. This resistance to aging or reversion of density relates to the stability of intrafiber crosslinks formed using polymeric polycarboxylic acid crosslinking agents. In contrast, cellulose fibers crosslinked with citric acid show a considerable increase in density, accompanied by a loss of bulk and absorbent capacity over time. Generally, the increase in density indicates a decrease in the level of crosslinking (i.e., reversion) in the fibers. In addition to density increase, the loss of crosslinking in the fibrous web results in a less bulky web and, consequently, diminished absorbent capacity and liquid acquisition capability. Accordingly, the present invention provides a method for forming cellulose fibers having stable intrafiber crosslinks that includes crosslinking cellulosic fibers with a polymeric polycarboxylic acid crosslinking agent as described above. Typically, the polymeric polycarboxylic acid crosslinked fibers have a reverted density increase of less than about 20% and, more preferably, less than about 10%. In contrast, citric acid crosslinked fibers have a reverted density increase of about 50%, which is significantly greater than the reverted density value of the fibers formed in accordance with the present invention. The effect of aging (i.e., reversion of crosslinking) on the density of fibrous webs composed of polyacrylic acid crosslinked fibers and fibrous webs composed of citric acid crosslinked fibers is described in Example 11. In addition, the wet bulk and absorbent capacity of polymaleic acid crosslinked fibers remain substantially unchanged in accelerated aging processes, indicating that fibers crosslinked with polymaleic acid also retain their crosslinks.
In another aspect of the present invention, a method for forming crosslinked fibers having a low knot level is provided. In the method, cellulosic fibers are crosslinked with a polymaleic acid polymer as generally described above. The resulting polymaleic acid crosslinked fibers typically have a knot level of less than about 10%, preferably less than about 5%. Fibers crosslinked with a representative urea-based crosslinking agent, DMDHEU, have a knot level of about 20%, which is significantly greater than the knot level of fibers formed in accordance with this invention. A comparison of knot level for polymaleic acid and DMDHEU crosslinked fibers is described in Example 7.
In another embodiment, the present invention provides cellulose fibers that are crosslinked with a blend of crosslinking agents that include the polymeric polycarboxylic acid described above and a second crosslinking agent. Preferably, the fibers are crosslinked with a second crosslinking agent having a cure temperature below that of the polymeric polycarboxylic acid. For this embodiment, suitable second crosslinking agents have a cure temperature below the cure temperature of the polymeric polycarboxylic acid crosslinking agents, i.e., below about 320xc2x0 F. Preferred second crosslinking agents include urea-based derivatives such as, for example, methylolated urea, methylolated cyclic ureas, methylolated lower alkyl substituted cyclic ureas, dihydroxy cyclic ureas, lower alkyl substituted dihydroxy cyclic ureas, methylolated dihydroxy cyclic ureas. Other suitable urea derivatives include dimethyldihydroxy urea (DMDHU, 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone), dimethyloldihydroxyethylene urea (DMDHEU, 1,3-dihydroxymethyl-4,5-dihydroxy-2-imidazolidinone), dimethylol urea (DMU, bis[N-hydroxymethyl]urea), dihydroxyethylene urea (DHEU, 4,5-dihydroxy-2-imidazolidinone), dimethylolethylene urea (DMEU, 1,3-dihydroxymethyl-2-imidazolidinone), and dimethyldihydroxyethylene urea (DDI, 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone).
Other preferred second crosslinking agents include polycarboxylic acids including, for example, citric acid, tartaric acid, maleic acid, succinic acid, glutaric acid, citraconic acid, maleic acid (and maleic anhydride), itaconic acid, and tartrate monosuccinic acid. In more preferred embodiments, the second crosslinking agent is citric acid or maleic acid (or maleic anhydride). Other preferred second crosslinking agents include glyoxal and glyoxylic acid.
While the composition of the crosslinking blend can be varied to form crosslinked cellulosic fibers having desired properties, the polymeric polycarboxylic acid is the predominant crosslinking agent in the blend. The second crosslinking agent is generally present in the blend in the amount of from about 5 to about 50 percent by weight of the total crosslinking blend.
The characteristics of representative crosslinked cellulose fibers prepared from blends of polyacrylic acid and maleic acid and polyacrylic acid and citric acid are described in Examples 3 and 10, respectively. Generally, the bulk and absorbent capacity of cellulose fibers crosslinked with polymeric polycarboxylic acid blends is greater than fibers crosslinked with either the polycarboxylic acid or the second crosslinking agent alone. Furthermore, the problem associated with discoloration to crosslinked fibers crosslinked with citric acid alone is improved by using a polymeric polycarboxylic acid blend without sacrificing the beneficial aspects of the fibers"" absorbent capacity. Cellulosic fibers crosslinked with a blend of a polymeric polycarboxylic acid and citric acid have been found to have improved brightness relative to fibers crosslinked with citric acid alone. In addition, the resistance of polymeric polycarboxylic acid crosslinked fibers to reversion, i.e., the loss of crosslinks, imparts stability to fibers crosslinked with polymeric polycarboxylic acid blends. For example, while cellulose fibers crosslinked with citric acid alone are highly susceptible to crosslink reversion, fibers crosslinked with blends of citric acid and a polymeric polycarboxylic acid exhibit advantageous absorbent properties and stable crosslinks.
The following examples are provided for the purposes of illustration, and not limitation.